Automation-Accelerated Electrolyte Design Mitigates Solubility Competition between Redox-Active Molecules and Supporting Salts

In nonaqueous redox-flow batteries (NRFBs), redox-active organic molecules (ROMs) and supporting salts compete for solvation sites, limiting achievable energy density. We combine automated high-throughput experimentation (HTE) with camera-based saturation monitoring and quantitative NMR to measure paired (ROM, salt) solubilities across single and mixed organic solvents. Using 2,1,3-benzothiadiazole (BTZ) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a model system, we find that a binary m-xylene/acetonitrile mixture dissolves ≈3 M of both BTZ and LiTFSI─surpassing the previously reported 2 M ceiling for neat acetonitrile─by leveraging complementary solvation (MX is BTZ-philic and salt-phobic; ACN stabilizes LiTFSI). A random-forest model (RMSE ≈ 0.24) trained on solvent descriptors highlights log P and salt concentration as dominant predictors and predicts MX/ACN ≈0.3/0.7 (v/v) to be near-optimal. These formulations retain practical viscosity and ∼5 mS·cm–1 conductivity at high loading. The workflow provides a reproducible, data-centric route to NRFB electrolyte design and motivates an open, standardized dual-solute solubility resource for accelerated electrolyte discovery.